N-aminoimides of halo-substituted polyhydromethanonaphthalenedicarboxylic acids



United States atent Qfiice 3,371,4i97 Patented Feb. 27, 1968 3,371,097N-AMINOlh HDES F HALO-SUBSTITUTED POLY- HYDROMETHANONAPHTHALENEDICARBOX.YLZC ACHDS Henryk A. Cyba, Evanston, 11]., assignor to Universal OiiProducts Company, Des Plaines, Ili., a corporation of Delaware NoDrawing. Continuation-impart of application Ser. No. 421,665, Dec. 28,1964. This application Sept. 28, 1966, Ser. No. 582,543

11 Claims. (Cl. 260-326) ABSTRACT OF THE DESCLOSURE N-aminoimides of achloro or bromo-substituted polyhydromethanonaphthalenedicarboxylicacid, exemplified by N-phenyl-aminoimide of5,6,7,8,9,9-hexachloro-1,2,3, 4,4a,5,8,8a octahydro 5, 8 methano-2,3-naphthalenedicarboxylic acid. The compounds are useful asshrinkproofing agents for fibrous materials such as wool, also as flameretardants for epoxy resins.

This application is a continuation-in-part of my copending applicationSer. No. 421,665, filed Dec. 28, 1964, now abandoned. This inventionrelates to novel compositions of matter comprising N-aminoimides ofcertain polycyclic acids and more particularly to novel compositions ofmatter comprising N-aminoimides of halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids.

Certain novel compositions of matter comprising -aminoimides ofhalo-substituted polyhydrornethanonaphthalenedicarboxylic acids whichare prepared according to the process hereinafter set forth in greaterdetail will find a Wide variety of uses in the chemical field. Forexample, an N-aminoimide of a halo-substitutedpolyhydromethanonaphthalenedicarboxylic acid may be used as one of thematerials in an interfacial polymerization process which is useful inimparting shrink-proofing properties to fibrous materials andparticularly to wool. The interfacial polymerization process is effectedby treating the fibrous material with an N-aminoimide of apolyhydromethanonaphthalenedicarboxylic acid and thereafter by treatingthe fibrous material with a polyacid polyhalide containing at least twoacid halide groups per molecule, both the N-arninoimide and polyacidpolyhalide being in solutions which are mutually immiscible with oneanother. The formation of the polymer on the fibrous material, andparticularly wool, will impart a shrink-proofing property on thematerial as well as any other desirable physical characteristics,including smoothness after drying, excellent hand, increased breakstrength and tear strength as well as improved resistance to abrasion,chemicals and pilling. The use of the aminoimides of the presentinvention as one of the reactants in forming the polymer is advantageousinasmuch as the fibrous material, and particularly wool, after treatmentthereof will not have the desirable characteristics of the fibrousmaterial altered nor will a post-cure of the material be necessary.

It has also been discovered that the products of the present inventionwhich comprise N-aminoimides ofpolyhalopolyhydromethanonaphthalenedicarboxylic acids are particularlyuseful as additives to certain polymeric compositions of matter andparticularly resins. The N-aminoimides of the present invention whenadded to these resins, and specifically resins which are referred to asepoxy resins, Will act as curing agents therefor and impart usefulproperties to the cured resins. For example, an epoxy resin which hasbeen cured by the addition of an N-aminoimide prepared according to theprocess hereinafter described in greater detail Will be fire resistantor retardant,

the resin being self-extinguishing when removed from the direct actionof a flame. This property being fire resistant will be especially usefulwhen preparing articles of commerce which are to be used in places whichmay be subject to excessive heat or the action of a flame.

In addition, another use to which the N-aminoimides of thehalo-substituted polyhydromethanonaphthalenedicarboxylic acids may beput include their use as extreme pressure additives for greases andlubricants, preparation of insecticides Which are useful againsthouseflies, red spiders, aphids and scale insects.

It is therefore an object of this invention to provide novelcompositions of matter which will find a Wide variety of use in thechemical industry.

A further object of this invention is to provide novel compositions ofmatter comprising certain N-aminoimides of halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids.

In a broad aspelt, an embodiment of this invention is found in anN-aminoimide of a chloroor bromo-substitutedpolyhydromethanonaphthalenedicarboxylic acid.

A further embodiment of this invention is found in an N-arylaminoimideof a chloroor bromo-substituted polyhydromethanonaphthalenedicarboxylicacid.

A specific embodiment of this invention is found in theN,N-diphenylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,-8,8a-octahydro 5,8 methano 2,3-naphthalenedicarboxylicacid.

Other objects and embodiments will be found in the fol lowing furtherdetailed description of this invention.

As hereinbefore set forth, the present invention is concerned with novelcompositions of matter comprising N-aminoimides of halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids. These compounds may beprepared in a manner hereinafter set forth in greater detail bycondensing a compound selected from the group consisting ofhalo-substituted polyhydromethanonaphthalenedicarboxylic acids andanhydrides thereof with a hydrazine at condensation conditions and inthe presence of a substantially inert organic solvent to prepare thedesired N-aminoimides. For purposes of this invention, the termN-aminoimide as used in the present specification and appended claimswill refer to unsubstituted N-aminoimides and substituted N-aminoimidesin which the nitrogen atom may contain substituents of a type alsohereinafter set forth in greater detail.

The halo-substituted polyhydromethanonaphthalenedicarboxylic acid oranhydride thereof which comprises one of the starting materials utilizedin the process of the present invention may be prepared in any suitablemanner such as the Diels-Alder reaction of a conjugated aliphatic dienewith an olefinic dicarboxylic acid or anhydride thereof. Examples ofconjugated aliphatic dienes which may be used include 1,3-butadiene,2-methyl-1,3-pentadiene, 1,3-pentadiene, etc.; olefinic dicarboxylicacids or anhydrides which may be used include maleic anhydride, methylmaleic anhydride, fumaric acid, maleic acid, itaconic acid, etc. TheDiels-Alder condensation will take place at an elevated temperature inthe range of from about to about 250 C. or more and at a pressuresufiicient to maintain a major portion of the reactants in a liquidphase, said pressure being in a range of from about atmospheric to aboutatmospheres or more. The tetrahydrophthalic acid or anhydride thereofwhich results from the aforementioned condensation is then furthercondensed with a conjugated halo-substituted cycloalkadiene to form thedesired product, examples of said halo-substituted cycloalkadienesinclude tetrachlorocyclopentadiene, hexachlorocyclopentadiene,tetrabromocyclopentadiene, hexabromocyclopentadiene, etc. The secondcondensation reaction is also effected at elevated temperatures in therange of from about 50 to about 250 C., or more and at pressures rangingfrom atmospheric up to about 100 atmospheres or more, the pressure againbeing sufiicient so as to maintain a major portion of the reactants inthe liquid phase at the reaction temperature. Examples ofhalo-substituted polyhydrornethanonaphthalenedicarboxylic acid oranhydrides thereof which may be utilized as a starting material in thepresent process include5,6,7,8,9,9hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-

methano-Z,3-naphthalenedicarboxylic acid,5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8a-ctahydro-5,8-

methano-Z,3-naphthalenedicarboxylic acid anhydride,5,6,7,8,9,9-hexabromo-1,2,3,4,4a,5,8,8a-octahydro-5,8-

methane-2,3-naphthalenedicarboxylic acid anhydride,5,6,7,8-tetrachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-

methano-Z,3-naphthalenedicarboxylic acid,5,6,7,8-tetrachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-

methano-Z,3-naphthalenedicarboxylic acid anhydride,5,6,7,8-tetrabromo-1,2,3,4,4a,5,8,8a-octahydro-5,8-

methano-Z,3-naphthalenedicarboxylic acid anhydride.

These compounds so listed are only representative of the class ofcompounds which may be prepared, and the present invention is notnecessarily limited thereto.

It is to be understood that the term halo-substitutedpolyhydromethanonaphthalenedicarboxylic acid or anhydride thereof, asutilized in the present specification and appended claims will refer toacids or anhydrides which may contain mono-, or polyhalo substitution.For purposes of brevity, the examples of compounds utilized in thisprocess are listed as containing more than one chlorine or brominesubstituent, although the actualnumber of halo substituents may rangefrom 1 up to about 8 or more.

The hydrazines which are condensed with the aforementionedhalo-substituted polyhydromethanonaphtbalenedicarboxylic acid anhydridespossess the generic formula:

in which R is selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, alkaryl and aralkyl radicals. It is to be noted thatthe hydrazine may be monoor di-substituted with the limitation beingthat one nitrogen atom must not contain a substituent other than twohydrogen atoms thereon. Examples of hydrazines which may be utilizedinclude hydrazine, alkyl-substituted hydrazines such as methylhydrazine,ethylhydrazine, propylhydrazine, isopropylhydrazine,N',N'-dimethylhydrazine, N,N-diethylhydrazine, -N',N'-dipropylhydrazine,mixed alkyl aryl hydrazines such as N-methyl-N-phenylhydrazine,N-ethyl-N-phenylhydrazine, N-isoamy1-N- phenyl, N-isobutyl-N'-phenyl,N-methy1-N-toly1, N'-ethyl-N'-tolyl, N-methyl-N-benzylhydrazine, etc.;cycloalkyl-substituted hydrazines such as cyclopentylhydrazine,cyclohexylhydrazine, cycloheptylhydrazine, N',N-dicyclopentylhydrazine,N,N-dicyclohexylhydrazine, N',N-dicycloheptylhydrazine, etc.;aryl-substituted hydrazines such as phenylhydrazine,N,N-diphenylhydrazine, etc.; alkaryl-substituted hydrazines such asp-tolylhydrazine, N',N-di-(p-tolyl)hydrazine, p-ethylphenylhydra'zine,N, N'-di-(p-ethylphenyl)hydrazine, etc.; aralkyl-substituted hydrazinessuch as benzylhydrazine, N',N'-di-benzylhydrazine, etc. It is to beunderstood that the aforementioned hydrazines and substituted hydrazinesin which the substituents are on only one of the nitrogen atoms are onlyrepresentative of the class of compounds which may be used, and that thepresent invention is not necessarily limited thereto. It is alsounderstood that the alkyl, cycloalkyl or aryl substituents may containadditional halogens, alkoxy, amino, alkylamino, hydroxyl, carbonyl orester, etc., groups.

The reaction between the halo-substituted polyhydromethanonapthaleuedicarboxylic acid anhydride and the particular hydrazine iseffected at elevated temperatures ranging from about up to about 200 C.or more, the particular reaction temperature being dependent upon thenature of the substantially inert organic solvent in which the reactionis effected and the particular hydrazone used as a co-reactant. Thuswith N-ethyl-N'-phenylhydrazine, N-isoamyl-N'-phenylhydrazine,N'-isobuty1- N'-phenylhydrazine, N-methyl-N'-phenylhydrazine, N,N-diphenylhydrazine, etc., the reaction is effected in the presenceofrelatively high boiling solvents such as benzcne, toluene, xylene,ethylbenzene, cumene, etc., in the temperature range of from about 80 toabout C. Examples of substantially inert organic solvents which may beused include paraffinic hydrocarbons such as n-pentane, n-hexane,n-heptane, etc.; cycloparafilnic hydrocarbons such as cyclopentane,cyclohexane, methylcyclopentane, etc.; aromatic hydrocarbons such asbenzene, toluene, benzelenes, ethylbenzenes, etc. When low boilingsubstitutedhydrazines constitute one of the reactants in the presentprocess, it is preferable to use solvents in which both reactants aresoluble. Examples of these solvents include acetic acid, dimethyl ether,diethyl ether, dipropyl ether, dioxane, pyridine, alkyl pyridines,tetrabydrofurane, ethylene glycol ethers, polyethylene glycolpolyethers, etc. In addition, any nonreactive solvent which is inert tothe acid or anhydride and the hydrazines, or combination of solvents maybe utilized. Furthermore, it is contemplated within the scope of thisinvention that catalysts, either acidic or basic in nature, which areknown in the art to promote amidation or dehydration reactions such as;phosphorus trichloride, thionyl chloride, tributylamine, etc., may beused. The reaction will proceed for a period of time suflicient toazeotrope off the water which has been formed by the reaction.Therefore, the reaction time will, of necessity, be dependent to someextent upon the particular temperature which is employed (usually thereflux temperature of the solvent) and will range from about 0.5 up toabout 5 hours or more.

The process of the present invention which is utilized to prepare thenovel compositions of matter comprising N-a'rninoamides ofhalo-substituted polyhydromethanonaphthalenediacarboxylic acids may beeffected in any suitable m'aner and may comprise either a batch orcontinuous type operation. When a batch type operation is used, ahydrazine of the type hereinbefore set forth in greater detail is placedin an appropriate reaction vessel along with a substantially inertorganic solvent. The halosubstitutedpolyhydromethanonaphthalenedicarboxylic acid or anhydride thereof isslowly added thereto, the reaction usually being exothermic. To controlthis exothermicity, the hydrazine may be cooled prior to the addition ofthe acid or anhydride and the resulting rise in temperature controlledby utilization of any external cooling means such as an icebath. Uponcompletion of the addition of the acid or anhydride, the reactionmixture is heated to the reflux temperature of the solvent. The reactionvessel which is utilized for the process of the present invention, isprovided with means such as a water trap for removing the water which isformed during the reaction. Upon completion of the desired residencetime, which may, as hereinbefore set forth range from about 0.5 up to 5hours or more, as evidenced by the removal and recovery of thetheoretical amount of water, the reaction mixture is allowed to cool toroom temperature. Following this, the solvent may be removed bydistillation on a steambath or other similar apparatus, after which theexcess hydrazine compound, if any, is also removed, usually byfractional distillation. In this respect, it should be noted that thehydrazine or the substituted hydrazines are actually present in theoriginal reaction mixture in a ratioof from about 1.0 to about 2 molesof hydrazine per mole of anhydride. The reaction product is recoveredfrom the distillation and purified by conventional means such as washingwith Water, dissolving in alcohol and drying.

It is also contemplated within the scope of this invention that theN-aminoimides of halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids may be prepared in acontinuous manner of operation, although not necessarily with equivalentresults. When such a method is used, a quantity of the startingmaterials comprising the halo-substitutedpolyhydromethanonaphthalenedicarboxylic acid or anhydride thereof andthe hydrazine compound, along with a substantially inert organicsolvent, are continually charged to a reaction vessel which ismaintained at the proper operation conditions of temperature andpressure. Due to the exothermicity of the reaction, the reactants arecharged to the reactor through separate lines. Upon completion of thedesired residence time in the reaction vessel the reactor effluent iscontinually removed, the unreacted starting materials are separated fromthe efliuent by conventional means and recycled to form a portion of thefeed stock, while the remainder of the efiiuent is further subjected tofractional distillation to remove the solvent (the Water which is formedhaving previously been azeotroped off while the reaction mixture wasstill in the reaction vessel) and thereafter purified and recovered byconventional means. The novel compositions of matter of the presentinvention comprising N-aminoimides, N-alkylaminoimides, N-arylaminoimides, N-alkylarylaminoimides, -N-aralkylaminoimides,-N-alkarylaminoimides and N-cycloalkylaminoimides of halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids will possess the genericformula:

in which X is selected from the group consisting of hydrogen andhalogen, and particularly chlorine and/or bromine, at least two of theXs being halogen and R is selected from the group consisting ofhydrogen, alkyl, aryl, alk aryl, aralkyl and cycloalkyl radicals. Somespecific examples of N-aminoimides of halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids which may be preparedinclude the N-rnethyl-aminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8a-octahydro 5,8-methano-2,3- naphthalenedicarboxylic acid,

the N-ethylarninoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

the N-propyl-aminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

the N-dimethylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-rneth-ano-2,3- naphthalenedicarboxylicacid,

the N-diethylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

the N-phenylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-S,8-methano-2,3- naphthalenedicarboxylicacid,

the N-diphenylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8aoctahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

the N-phenylaminoimide of 5,6,7,8,9,9-hexabromo-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

the N-rnethylaminoimide of 5,6,7,8,9,9-hexabromo-1,2,3,4,4a,5,8,8a-octahydro-5,8-rnethano-2,3 naphthalenedicarboxylicacid,

the N-benzylaminoimide of5,6,7,8,9,9-hexachlorol,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid,

the N,N-dibenzylamino-imide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8methano-2,3- naphthalenedicar'boxylicacid,

the N-p-tolylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,Sa-octahydro-S,8-rnethano-2,3- naphthalenedicarboxylicacid,

the N,N-di(p-toiyl)aminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

N-cyclohexylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid,

the N,N-cyclohexylaminoimide of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid, etc.

It is to be understood that the aforementioned N-aminoimides of thehalo-substituted polyhydro-methanonaphthalenedicarboxylic acids are onlyrepresentatives of the class of novel compositions of matter and thatthe present invention is not necessarily limited thereto.

As a specific example of one of the uses to which an N-aminoimide of ahalo-substituted polyhydromethanonaphthalenedicarboxylic acid may beput, the following will describe the use as additives for certainpolymeric compositions of matter and particularly resinous material.Particularly speaking, the N-aminoirnides of the halo-substitutedpolyhydromethanonaphthalenedicarboxylic acids which are preparedaccording to the process of this invention may be used as additives withepoxy resins whereby the final product will posses advantageous physicalproperties, one of which is a high degree of flame retardancy. The epoxyresins in an uncured state are usually thermoplastic and may range fromlow viscosity liquids to high melting point, brittle solids. One exampleof an epoxy resin which may be cured by the addition of theN-aminoimides of the present invention is the condensation product ofepichlorhydrin and bisphenol-A. The resins may be cured by admixing animide of an acid of the type hereinbefore set forth with the resin andthereafter curing the mixture by treatment at an elevated temperaturefor a predetermined period of time. The resultant product will have thephysical characteristics thereof altered to their desirable values andthus may be utilized for various purposes such as floor surfacing,coatings, etc. Among these desirable characteristics is the excellentfire retardance as well as the color stability of the finished product.

The following examples are given to illustrate the process of thepresent invention which, however, are not intended to limit thegenerally broad scope of the present invention with strict accordancetherewith.

EXAMPLE I One method of preparing the compounds according to the processof the present invention is to place 91.5 g. (0.75 mole) ofN-methyl-N-phenylhydrazine in a reaction vessel provided with a Watertrap. During a period of about 1 hour, 213 g. (0.5 mole) of5,6,7,8,9,9-hexachloro- 1,2,3,4,4a,5,8,8a octahydro 5,8 methano 2,3naphthalenedicarboxylic acid anhydride is gradually added thereto.Following this, the mixture is agitated and heated to about C., 200 cc.of xylene is added, the reaction mixture is heated and maintained atreflux temperature (BS- C.) for a period of about 1.5 hours. During thistime, the water which is formed is azeotroped 011 during the refluxing.The xylene is then gradually distilled olf While the temperature isbeing raised to -l70 C. The residual Xylene and the excessN'-methyl-N-phenylhydrazine are then removed by distillation under ahigh vacuum. After removal of the solvent and excess hydrazine, thesolid which remains is ground to a fine powder, washed several timeswith water, dissolved in methyl alcohol and dried using anhydrous sodiumI? sulphate. The mixture is then filtered and the methyl alcohol isevaporated, thereby leaving the desired product which comprises theN-methyl-N-phenylarninoimide of 5,6,7,8,9,9 hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8- methano-Z,3-naphthalenedicarboxylicacid.

EXAMPLE II In an alternate method 54 g. of phenylhydrazine (0.5 mole) isdissolved in 100 g. of glacial acetic acid. This is then added to asolution of 213 g. (0.5 mole) of 5,6,7,8,9,9 hexachloro1,2,3,4,4a,5,8,8a octahydro-5,8- methano-Z,3-naphthalenedicarboxylicacid in acetic acid. The solution is refluxed and mixed for about 2hours. Thereafter, the product is precipitated with water, filtered off,dissolved in ether, dried with anhydrous sodium sulphate, filtered andthe ether and acetic acid are distilled off, the desired productcomprising the N-phenylaminoimide of 5,6,7,8,9,9 hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8-methan-2,3-naphthalenedicarboxylic acidbeing recovered.

EXAMPLE 111 To illustrate another method of obtaining the desiredproduct of the present invention, 108 g. (2.0 mole) of methylhydrazineis charged to a reaction flask provided with stirring and heating means,as well as a Dean-Stock adapter. The flask is imersed in an ice bathuntil the temperature of the methylhydrazine is lowered to about 3 C.Following this, 85 g. (0.2 mole) of 5,6,7,8,9,9- hexachloro1,2,3,4,4a,5,8,8a octahydro 5,8-methano- 2,3-naphthalenedicarboxylicacid anhydride is slowly added during a period of 15 minutes. Theimmediate reaction upon the addition of the anhydride will be exothermicwith the well temperature reaching about 15 C. during the addition. Thereaction mixture is then allowed to warm to room temperature and 200 cc.of ethyl ether is added. The compounds are refluxed with the ethyl etherfor 1 hour, then the ether is replaced by 100 g. of benzene and thereaction mixture refluxed for 2 hours. Finally, the benzene is replacedby xylene, the reaction mixture is then heated to reflux and maintainedthereat for a period of about 3 hours. The reaction is consideredcomplete when the theoretical amount of water is collected in theadapter. Following this, the solution is allowed to cool to roomtemperature and treated to a manner similar to that set forth in ExampleI above, the desired product comprising the N-methylaminoimide of5,6,7,8,9,9-hexachloro l,2,3,4,4a,5,8,8a octahydro 5,8 methane-2,3-naphthalenedicarboxylic acid being recovered.

EXAMPLE IV In this example, 92 g. (0.5 mole) of N,N'-diphenylhydrazineand 100 cc. of toluene along with 213 g. (0.5 mole) of 5,6,7,8,9,9hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acidanhydride are placed in a reaction flask of a similar nature to thosehereinbefore described. The reaction mixture is then heated to refluxtemperature (approximately 115- 120 C.) and maintained thereat for aperiod of about 4 hours. During this time, a substantial amount of thetheoretical water which is formed is recovered in the adapter. Tolueneis then gradualy distilled off and the temperature raised gradually to160l70 C. The refluxing and mixed mixture is maintained at thistemperature for 1 hour. The flask and contents thereof are then allowedto cool to room temperature, the residual toluene and the excessN',N-diphenylhydrazine are removed by distillation under reducedpressure, The desired product comprising the N,N-diphenylaminoirnide of5,6,7,8,9,9-hexachloro 1,2,3,4,4a,5,8,8a octahydro 5,8-methano-2,3-naphthalenedicarboxylic acid is recovered by conventional means.

8 EXAMPLE v In this example, 17.7 g. (0.2 mole) of N,N'-diethylhydrazineare placed in a reaction vessel which is thereafter cooled to atemperature of about 3 C., by immersing the flask in an ice bath. To thecooled mixture is added 42.6 g. (0.1 mole) of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboxylicanhydried during a period of about 15 minutes, The temperature of theflask will rise due to the exothermicity of the reaction and uponcompletion of the addition of the anhydride, the flask and contentsthereof are allowed to warm to room temperature. Following this cc. oftoluene are added, the flask and contents thereof are heated to atemperature of about C., and maintained thereat for a period of about 4hours, the reaction being completed when the theoretical amount of waterwhich is formed during the reaction is recovered in the water trap. Atthe end of this time, the flask and contents thereof are allowed to coolto room temperature. The solvent is removed by distillation on a steambath and excess hydrazine removed by distillation under a high vacuum.The desired product comprising the N,N-diethylaminoimide of5,6,7,8,9,9-heXachloro-1,2,3,4,- 4a,5,8,8a octahydro 5,8methano-2,3-naphthalene-dicarboxylic acid is recovered.

EXAMPLE VI In this example, 53.4 (0.5 mole) of phenylhydrazine alongwith 200 cc. of toluene is placed in a reaction flask which isthereafter cooled by means of an ice bath. g. (0.25 mole) of5,6,7,8,9,9-hexabromo-l,2,3,4,4a,5a,8,8aoctahydro5,8-methano-2,3-naphthalenedicarboxylic anhydried is slowly added to themixture during a period of about 30 minutes. Upon completion of theaddition which is accompanied by a rise in temperature due to theexothermic nature of the reaction, the flask and contents thereof areheated to reflux temperature of about 115 C. and maintained thereat fora period of about 4 hours, the theoretical amount of water which isformed during the reaction being collected in a Water trap. Uponcompletion of the reaction, the flask and contents thereof are allowedto cool to room temperature, following which the toluene is removed bydistillation as is the excess phenylhydrazine. The desired productcomprising the N-phenylaminoimide of5,6,7,'8,9,9-hexabromo-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-Z,3-naphthalenedicarboxylic acid is recovered by conventionalmeans.

EXAMPLE VII In this example, 192 g. of hydrazine are dissolved in 500 g.of methanol and placed in a three neck two liter flask provided withstirring means and a nitrogen inlet tube. Gradually 425 g. of5,6,7,8,9,9-hexachloro-1,2,3,4,- 4a,5,8,8a octahydro 5,8methano-2,3-naphthalenedicarboxylic anhydride are added in aliquots,diminishing in size. The temperature is kept below the boiling point ofmethanol by cooling. At the end of the addition period, the mixture isrefluxed for one hour, most of the methanol being distilled off untilthe contact becomes mushy and difficult to stir. The product is thenfiltered, suspended in benzene and refluxed until no more evolution ofwater is evident. The product is filtered again, the mother liquor isevaporated until diflicult to stir and treated as above. If desired, thesecond mother liquor can be treated successively as above until most ofthe product is filtered off and the remaining liquid consists ofmethanol and hydrazine. This can be recovered if desired. The abovefiltered precipitates are washed with water, dried by azeotroping inbenzene and finally the benzene is evaporated. The second and thirdprecipitates so obtained are substantially the N-arninoimide of5,6,7,8,9,9-hexachloro-1,2,3,- 4,4a,5,8,8a octahydro 5,8 methano2,3-naphthalenedicarboxylic acid.

9 I claim as my invention: 1. A compound having the formula:

where X is chlorine or bromine; Y is hydrogen, chlorine or bromine; andR is selected from the group consisting of hydrogen, lower alkyl,phenyl, lower alkyl-substituted phenyl, phenyl-substituted lower alkyl,and cycloalkyl containing from 5 to 7 carbon atoms.

2. The compound of claim 1 being N,N-diphenylaminoimide of 5,6,7,8,9,9hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3naphthalenedicarboxylic acid.

3. The compound of claim 1 being N-phenylaminoimide of 5,6,7,8,9,9hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylicacid.

4 The compound of claim 1 being N-rnethylaminoimide of 5,6,7,8,9,9hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylicacid.

5. The compound of claim 1 being N,N-diethylamino- 2o imide of5,6,7,8,9,9 hexachloro1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylicacid.

6. The compound of claim 1 being N-methyl-N-phenylaminoimide of5,6,7,8,9,9hexachloro-l,2,3,4,4a,5,8,8aoctahydro-5,8-methano-2,3-naphthalenedicarboxylicacid.

7. The compound of claim 1 wherein at least one R is phenyl.

8. The compound of claim 1 wherein at least one R is lower alkyl.

9. The compound of claim 1 wherein at least one R is loweralkyl-substituted phenyl.

10. The compound of claim 1 wherein at least one R is phenyl-substitutedlower alkyl.

11. The compound of claim 1 wherein at least one R is cycloalkylcontaining 5 to 7 carbon atoms.

References Cited UNITED STATES PATENTS 3,305,347 2/1967 Minieri 71-1213,235,595 2/1966 Pawloski 71121 XR 3,197,504 7/1965 Harvey 71-121 XR3,138,521 6/1964 Jelinek et a1 71121XR 3,084,036 4/1963 Josephs 71-121XR 3,075,013 1/1963 Haldeman et al. 71-121 XR r ALEX MAZEL, PrimaryExaminer.

I. NARCAVAGE, Assistant Examiner.

